Luca Lusvarghi

Synthesis and characterization of praseodymium-doped ceria powders by a microwave-assisted hydrothermal (MH) route

Nanocrystalline Pr-doped ceria powders were prepared for the first time by a microwave-assisted hydrothermal route. The effect of the microwave treatment in relation to the conventional hydrothermal technique was evaluated. The samples prepared were characterized in terms of composition, crystalline structure, particle shape and size distribution by X-ray diffraction, transmission electron microscopy (TEM) and specific surface area analysis (BET). The color properties of these solid solutions were also evaluated as a function of synthesis conditions and composition. Finally the oxidation state of the Pr cations and the relative quantities of Pr(IV) and Pr(III) were investigated by X-ray absorption at the M4,5 Pr absorption edge.

Suspension thermal spraying of hydroxyapatite: microstructure and in vitro behaviour.

In cementless fixation of metallic prostheses, bony ingrowth onto the implant surface is often promoted by osteoconductive plasma-sprayed hydroxyapatite coatings. The present work explores the use of the innovative High Velocity Suspension Flame Spraying (HVSFS) process to coat Ti substrates with thin homogeneous hydroxyapatite coatings. The HVSFS hydroxyapatite coatings studied were dense, 27-37μm thick, with some transverse microcracks. Lamellae were sintered together and nearly unidentifiable, unlike conventional plasma-sprayed hydroxyapatite. Crystallinities of 10%-70% were obtained, depending on the deposition parameters and the use of a TiO2 bond coat. The average hardness of layers with low (<24%) and high (70%) crystallinity was ≈3.5GPa and ≈4.5GPa respectively. The distributions of hardness values, all characterised by Weibull modulus in the 5-7 range, were narrower than that of conventional plasma-sprayed hydroxyapatite, with a Weibull modulus of ≈3.3. During soaking in simulated body fluid, glassy coatings were progressively resorbed and replaced by a new, precipitated hydroxyapatite layer, whereas coatings with 70% crystallinity were stable up to 14days of immersion. The interpretation of the precipitation behaviour was also assisted by surface charge assessments, performed through Z-potential measurements. During in vitro tests, HA coatings showed no cytotoxicity towards the SAOS-2 osteoblast cell line, and surface cell proliferation was comparable with proliferation on reference polystyrene culture plates.

Comparison between plasma- and HVOF-sprayed ceramic coatings. Part I: microstructure and mechanical properties

Few papers deal with High Velocity Oxygen-Fuel (HVOF) sprayed ceramics. This two-part study thoroughly compares HVOF sprayed Al2O3, nanostructured Al2O3, Cr2O3 to Atmospheric Plasma Sprayed (APS) ones. The first part discusses microstructure and micromechanics. HVOF-sprayed ceramics achieve superior cohesion (lower porosity and lower average pore area). Size effects in Vickers microindentation tests are different for HVOF and APS ceramics. At 1 N load, hardness is higher for HVOF coatings (no cracking). Under 5 N and 10 N loads, hardness decreases gradually for HVOF coatings; APS coatings are largely cracked at 5 N. HVOF-sprayed ceramics are tougher than APS ones and have higher elastic modulus.

HyFlex EDM: superficial features, metallurgical analysis and fatigue resistance of innovative electro discharge machined NiTi rotary instruments

AIM To evaluate the surface and microstructural alterations of new and used HyFlex EDM prototypes and to test their fatigue resistance. METHODOLOGY Fifteen HyFlex EDM prototypes were used for in vitro instrumentation of severely curved root canals. Surface and microstructural characteristics of new and used files were compared by ESEM analysis equipped with energy dispersive X-ray spectrophotometry (EDS) and optical metallographic imaging. Usage-induced degradation was assessed. Thirty additional HyFlex EDM prototypes and 20 standard manufactured HyFlex CM files were subjected to cyclic fatigue tests. Time to fracture was recorded, and results were validated using the Kruskal-Wallis test (α-level 0.05). Fatigued files were analysed by ESEM for fractographic evaluation. RESULTS Surface and microstructural characterization of EDM prototypes revealed the typical spark-machined surface of a NiTi EDM alloy. No fractures were registered during root canal instrumentation. No evident surface alterations and minor degradation were observed between new and used instruments. The metallographic analysis of new and used files disclosed a homogeneous structure, mostly composed of lenticular martensite grains, and some residual austenite. The cyclic fatigue test showed an increase of fatigue resistance up to 700% on the EDM compared to CM files. CONCLUSIONS Spark-machined peculiar surface is the main feature of HyFlex EDM. Low degradation was observed after multiple canal instrumentations. Prototypes exhibited surprising high values of cyclic fatigue resistance and a safe in vitro use in severely curved canals.

Engineering the Microstructure of Solution Precursor Plasma-Sprayed Coatings

This study examines the fundamental reactions that occur in-flight during the solution precursor plasma spraying (SPPS) of solutions containing Zr- and Y-based salts in water or ethanol solvent. The effect of plasma jet composition (pure Ar, Ar-H2 and Ar-He-H2 mixtures) on the mechanical break-up and thermal treatment of the solution, mechanically injected in the form of a liquid stream, was investigated. Observation of the size evolution of the solution droplets in the plasma flow by means of a laser shadowgraphy technique, showed that droplet break-up was more effective and solvent evaporation was faster when the ethanol-based solution was injected into binary or ternary plasma gas mixtures. In contrast with water-based solutions, residual liquid droplets were always detected at the substrate location. The morphology and structure of the material deposited onto stainless steel substrates during single-scan experiments were characterised by SEM, XRD and micro-Raman spectroscopy and were shown to be closely related to in-flight droplet behaviour. In-flight pyrolysis and melting of the precursor led to well-flattened splats, whereas residual liquid droplets at the substrate location turned into non pyrolysed inclusions. The latter, although subsequently pyrolysed by the plasma heat during the deposition of entire coatings, resulted in porous “sponge-like” structures in the deposit.

Heat Treatment Effects on the Tribological Performance of HVOF-Sprayed Co-Mo-Cr-Si Coatings

The tribological behavior of high-velocity oxyfuel sprayed Co-28%Mo-17%Cr-3%Si coatings, both assprayed and after heat treatments at 200, 400, and 600 °C for 1 h, has been studied. The as-sprayed coating contains oxide stringers and is mostly amorphous. It has low hardness (∼6.7 GPa) and toughness and undergoes adhesive wear against 100Cr6 steel. The friction coefficient increases up to ∼0.9, so the flash temperature reaches a critical oxidation value; then, friction decreases and increases again. This phenomenon occurs periodically. Much adhesive wear occurs in the first stage. Abrasive wear prevails against alumina pin: the coating wear rate is lower because it possesses good plasticity. Thermal effects still occur. The 600 °C treatment causes formation of submicrometric crystals. Hardness increases (∼8.8 GPa), adhesive wear is prevented, the friction coefficient has no peaks. Against the alumina pin, wear rates remain similar to the as-sprayed case. Nevertheless, the friction coefficient has no peaks and its final value is lowered (from 0.84 to 0.75).

High-Pressure Cold-Sprayed Ni and Ni-Cu Coatings: Improved Structures and Corrosion Properties

Cold spraying is a promising technique for the production of dense metallic coatings. In cold spraying, coating formation is through high velocity impacts of solid particles with high kinetic energy. During impact, particles deform plastically and adhere to the substrate, gradually building-up the coating. This makes it possible to form pure and dense coating structures. These impermeable coatings are advantageous in many applications such as those where corrosion protection is required. Nickel and nickel-copper alloys have good corrosion resistance and therefore, as dense coatings, have high potential for employment as corrosion barrier layers. In this study, the structural and corrosion properties of high-pressure cold-sprayed (HPCS) Ni and NiCu coatings are characterized. NiCu alloys are known to have good corrosion resistance in sulphuric and hydrochloric acids, whereas Ni is resistant to caustic soda and alkaline salt solutions. This study also shows the effect of heat treatments on coating properties. FESEM studies of cross-sectional samples reveal structural details of the HPCS coatings while corrosion properties are evaluated with polarization measurements. The corrosion behavior of both the bulk and substrate material is determined in order to assess the real corrosion protection potential of the coatings.

The structure of ZrO2 phases and devitrification processes in a Ca–Zr–Si–O-based glass ceramic: a combined a-XRD and XAS study

The structure of the Zr atomic environment in a CaO-ZrO 2 -SiO 2 glass ceramic as a function of thermal treatments has been studied, combining X-ray absorption spectroscopy (XAS), X-ray diffraction (XRD) and anomalous XRD (a-XRD) techniques. The analysis of XRD patterns demonstrates that the devitrification process proceeds through the partial segregation of Zr-depleted phases (wollastonite-like) and Zr-rich phases (Zr oxides). The XAS and a-XRD measurements at the Zr K-edge have been exploited in order to obtain a closer insight into the atomic structure around the Zr atoms. In the as-quenched glass the Zr atom is sixfold coordinated to O atoms in an amorphous environment rich in Ca and Si. Thermal treatment firstly (T = 1273-1323 K) causes partial segregation of Zr in the form of an oxide with a tetragonal zirconia (t-ZrO 2 ) crystalline structure. Raising the temperature (T = 1373 K) causes the formation of ZrO 2 crystallites in the monoclinic crystallographic phase (baddeleyite, m-ZrO 2 ). Analysis of the XAS data shows that a considerable amount of Zr remains in an amorphous calcium silicate phase.

Comparison between plasma- and HVOF-sprayed ceramic coatings. Part II: tribological behaviour

This is the second part of comparative study between High Velocity Oxygen-Fuel (HVOF) flame-sprayed and Atmospheric Plasma-Sprayed (APS) ceramics. Dry particles abrasion test and dry sliding wear test at room temperature, 400?C and 700?C are performed. In dry sliding against SiC, at room temperature stable tribofilms are formed and mild wear (10-6 mm?/(Nm)) occurs for all coatings. When temperature and normal load increase, making brittle cracking a significant wear mechanism, HVOF coatings become superior to APS ones, thanks to higher toughness. In dry particles abrasion, brittle fracture prevails; therefore, the tougher HVOF coatings outperform APS ones.

Tribological Properties of Hard Metal Coatings Sprayed by High-Velocity Air Fuel Process

AbstractLowering the thermal energy and increasing the kinetic energy of hard metal particles sprayed by the newly developed HVAF systems can significantly reduce their decarburization, and increases the sliding wear and corrosion resistance of the resulting coatings, making the HVAF technique attractive, both economically and environmentally, over its HVOF predecessors. Two agglomerated and sintered feedstock powder chemistries, WC-Co (88/12) and WC-CoCr (86/10/4), respectively, with increasing primary carbides grain size from 0.2 to 4.0 microns, have been deposited by the latest HVAF-M3 process onto carbon steel substrates. Their dry sliding wear behaviors and friction coefficients were evaluated at room temperature via Ball-on-disk (ASTM G99-90) wear tests against Al2O3 counterparts, and via Pin-on-disk (ASTM G77-05) wear tests against modified martensitic steel counterparts in both dry and lubricated conditions. Sliding wear mechanisms, with the formation of wavy surface morphology and brittle cracking, are discussed regarding the distribution and size of primary carbides. Corrosion behaviors were evaluated via standard Neutral Salt Spray, Acetic Acid Salt Spray, accelerated corrosion test, and electrochemical polarization test at room temperature. The optimization of the tribological properties of the coatings is discussed, focusing on the suitable selection of primary carbide size for different working load applications.